Corandomized margarine oils



United States Patent Ofifice 3,353,964 CORANDOMIZED MARGARHNE OlLS PaulSeiden, Burlington, Ontario, Canada, assignor to The Procter & GambleCompany, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Aug.21, 1964, Ser. No. $1,293 Claims priority, application Canada, Sept. 23,1963, 885,132, Patent 718,373 5 Claims. (Cl. 99--118) The presentinvention relates to the preparation of margarine oil and, moreparticularly, to margarine oil containing corandomized triglycerides ofcertain short chain and long chain fatty acid in proportions and amountswhich impart improved properties to the margarine oil and, consequently,to margarine prepared therefrom.

One preferred aspect of this invention relates specifically to anadditive for margarine oil which is a corandornized blend ofhydrogenated rapeseed oil with coconut and/ or palm kernel oil. Anotherparticularly preferred aspect of this invention relates to a specialmargarine oil comprising a mixture of hydrogenated rapeseed oil, palmoil and coconut oil, which mixture is then corandomized.

Margarine consists of an emulsion of two phases, one of these beingfatty in nature while the other is aqueous in nature. The physicalcharacteristics of a finished margarine such as firmness, spreadability,and ease of melting in the mouth, are to a large extent determined bythe characteristics of the oil, or fatty, constituent which makes up thefatty phase of the emulsion. These characteristics are to a large extentdependent on the percentages of the fatty matter which exist in thesolid state at the various temperatures normally encountered during thestorage, use and consumption of the margarine.

For example, the margarine should melt readily in the mouth to avoid asensation of waxiness or stickiness and to have a satisfactory flavor.This means there must be almost no fatty material in the solid state ator near body temperatures. On the other hand, at temperatures of use itmust be capable of being spread and this requires that some portion ofthe fatty material be in the solid state at that temperature, but not somuch that the margarine is hard and difficult to spread and not solittle that the margarine will slump or lose its shape.

In addition, it is usually preferred to produce a margarine product thatduplicates or approaches the character istics of butter. In general,however, margarines are formulated to have better physical stability athigh temperatures than butter and therefore can be stored in bothrefrigerated or non-refrigerated storage. In specific cases margarinescan be produced deliberately diiferent from butter in othercharacteristics; i.e. margarines can be made spreadable at refrigeratedtemperature.

When some margarines are heated above about 70 F., part of their liquidoil content may start to seep or oiloff from the body of the margarineto the lower surfaces. This seepage increases with increase intemperature. If it becomes excessive, liquid oil can leak through theparchment wrap, soiling it as well as the outside carton and case. Inaddition to making the package unsightly and oily to the touch, the oilis more susceptible to rancidity because of the greater exposure of theoil to the air. Further, since margarine contains an aqueous phase,bacterial or mold contamination can also occur.

It is generally recognized therefore that margarines must havesuificient heat resistance to resist oil-off under trade conditions.

The conventional way of improving heat resistance of a margarine is toincrease the higher melting saturated or trans fatty acid glyceridecontent by further hardening the margarine oil. However such anincrease, though improving the heat resistance of the margarine, resultsin an increased solids content and hence a significant loss in theeating quality or melt in the mouth characteristics of the margarine.

The solids content referred to hereinabove is expressed, at diiferenttemperatures, in terms of a Solid Contents Index (SCI) which is measuredby what is essentially the test described in The Journal of the AmericanOil Chemists Society, March 1954, volume XXXI, pages 98-103. The testinvolves a dilatometric measurement of the amount by which a fat expandswhen heated from a specific temperature to complete melting. Since thisexpansion is due to both a volume increase when solids change to liquidswithout a temperature change and a volume increase due to thermalexpansion without change in phase from solid to liquid, allowance ismade for the thermal expansion so that the change in volume gives ameasure of the amount of solid phase present at the temperature ofmeasurement. The test has been modified in that readings are taken after30 minutes at the temperature of measurement.

SCI data for an oil are usually presented in the form of a curve inwhich the SCI is plotted against temperature. It is readily apparentthat a fiat SCI curve is undesirable for a margarine oil since it isnecessary to have a change within a small temperature range from aplastic material to one that is essentially a liquid.

One feature of the present invention is the addition to margarine oilsof an additive which while providing improved heat resistance tends tocause only a small increase in the solids content. By this feature, amargarine can be obtained which sacrifices far less eating quality thanhas been the case in the past. Since there is a definite relationshipbetween the heat resistance, eating quality or melt in the mouthcharacteristics and spreadability properties of margarine, it ispossible, by the present invention, to produce margarine with bettereating qualities and/or spreadability particularly for use in coldergeographic areas Where less heat resistance is required. Thus, thepresent invention makes it possible to provide other improvements inaddition to an improvement in heat stability.

In formulating margarine, soft oils can be hydrogenated and blended toprovide good performance characteristics in eating quality, heatresistance, and spreadability. These soft oils include soybean oil,cottonseed oil, corn oil, sunflower oil, and peanut oil. However,certain other oils, particularly palm oil, coconut oil, and palm kerneloil generally cannot be used as major components in a blended margarine(that is, in an nninteresterified or non-randomized margarine) since,when mixed with soft oils, they tend to harm the performancecharacteristics of the margarine, particularly the heat resistance andeating quality. Therefore, use at palm oil, coconut oil, and palm kerneloil in margarine has been very limited.

At certain times and in certain geographical areas it may beeconomically desirable to use a mixture of palm oil and coconut oil as amajor constituent of a margarine oil. One of the advantages of thisinvention is that it provides a means for using such a mixture of oilsin margarine.

By another feature of the present invention, margarine formulations canbe developed having increased quantities of palm oil, coconutoil,.and/or palm kernel oil. Thus, greater flexibility in formulationcan be achieved and high quality margarines can be composed witheconomically priced components depending on fluctuations in oil prices.

Patented Nov. 21, 1967 I been found that such technique may be improvedin order to provide a better balance of eating quality versus heatstability for a wide variety of margarine formulations. Thus, in orderto obtain a given heat stability, the use of the improved additive ofthe present invention in a margarine oil formula also provides improvedeating quality compared to previous margarine formulations. Conversely,in order to obtain a given eating quality, the use of the improvedadditive of the present invention provides a better heat stability in amargarine compared to previous margarine formulation.

While it is a principal feature or object of the present invention toprovide a margarine oil for preparing margarine having improved heatresistance, it is another feature of the present invention to provide amargarine oil for producing margarine having improved spreadingcharacteristics at low temperatures.

Still another object of the present invention is the provision of amargarine oil containing a soft oil, for example, soybcan oil, and palmoil in which more palm oil is incorporated than heretofore possible toyield a margarine of improved quality.

Yet another object of the present invention is the provision of amargarine oil containing coconut oil and palm kernel oil in which morecoconut oil is incorporated than heretofore possible to yield amargarine of improved quality.

A still further object of the present invention lies in the provision ofa margarine oil whereby a margarine is prepared having improvedpolymorphic crystal stability; in other words, a margarine is made moreresistant to texture changes and physical breakdown due to change in thetype of fat crystals.

A further object of the present invention lies in the provision of amargarine oil whereby a margarine is prepared having an improved balanceof eating quality versus heat stability.

A still further object of the present invention lies in the provision ofa margarine oil whereby a margarine having good quality and heatstability is prepared from higher levels of palm oil and coconut oilthan has hereto fore been possible.

In its broad aspects the present invention provides a margarine oiladapted to be manufactured into a margarine of good spreadability,oil-off, slump and eating qualities, the margarine oil comprising atleast about by weight of corandomized triglycerides containing saturatedshort chain fatty acids having from 6 to 14 carbon atoms and saturatedlong chain fatty acids having from 20 to 22 carbon atoms, the amount ofthe saturated long chain fatty acids being about 0.3 to about 5% byweight of the margarine oil and the ratio of the saturated short chainfatty acids in the margarine oil to the saturated long chain fatty acidsin the margarine oil being from 100:1 to 1:1. When the saturated longchain fatty acids are present in the margarine oil below about 0.3% byweight of the oil, there is a beneficial effect but it is very small andof no practical importance. Above about 5% by weight of the margarineoil, little additional practical improvement is found in the margarineattributable to the presence of the saturated long chain fatty acidswhich are present. The most practical and the most preferred limits areabout 1 to about 4% by weight of the margarine oil of saturated longchain arachidic and/or behenic acid with the ratio of short chain fattyacids containing 6 to 14 carbon atoms to these long chain fatty acidscontaining 20 to 22 carbon atoms being from 40:1 to 2:1. The long-chainarachidic and/or behenic acids should preferably be combined in atriglyceride molecule by corandomization with short chain fatty acids.Optimum benefits are achieved by maximizing the number of triglycerideswhich contain both long and short chain fatty acids and by minimizingthe triarachidic and tribehenic triglycerides. The corandomizedtriglycerides which contain arachidic acid and/or behenic acid and shortchain fatty acids exhibit highly increased stiffening power and uniquethixotropic characteristics which permit formulation of margarine withunusually low solid content at room temperature and good heat stability.

The long chain fatty acids containing 20 to 22 carbon atoms, arachidicacid and behenic acid, respectively, are desirably obtained byhydrogenation of rapeseed oil, mustard seed oil, Wallflower seed oil,nasturtiurn seed oil, or marine oil. Rapeseed oil is the preferredsource of the long chain fatty acids. The hydrogenation is carried outunder the usual conditions of time, temperature and pressureconventional in the art in the presence of any suitable catalyst.Accordingly, details of the hydrogenation will not be given here. Thehydrogenation must be carried out until the oil has an iodine value(I.V.) of less than 30 and preferably less than 10, in order to achievethe advantages of the present invention.

Rapeseed oil or any of the other above-enumerated sources of long chainfatty acids which has been hydrogenated to an TV. less than 30 should beused in an amount which is more than 0.6% by weight of the margarine oilbut less than 25% by weight of the margarine oil. The greater the degreeof hydrogenation, and hence the lower the I.V., the more acid in the oilwill be converted to arachidic and/or behenic acid, and the lesshydrogenated oil will be required to be corandomized with an oiicontaining short chain fatty acids to give the same effect.

The present invention improves the characteristics of margarine preparedfrom margarine oils containing soy bean oil, cottonseed oil, corn oil,sunflower oil, safiiower seed oil, peanut oil and lard as well as thosemargarine oils in which tallow, palm oil, coconut oil, or palm kerneloil are used in amounts up to by weight. If the tallow, palm oil,coconut oil or palm kernel oil is corandomized with an oil containinglong chain fatty acids such as rapeseed oil, these oils can constituteup to about by weight of the margarine oil. A corandomized blend such asthis is simply mixed with an unhydrogenated or slightly hydrogenatedsoft oil; for example: 60% by weight soybean oil is blended with 40% byweight of a corandomized blend containing 12% by weight of thecorandomized blend of highly hydrogenated rapeseed oil having an I.V. ofabout 4 and 88% by weight of the corandomized blend of palm kernel oil.In other margarine oil formulations the entire margarine oil iscorandomized; for example: 38% by weight palm oil is corandomized with12% by weight highly hydrogenated rapeseed oil having an I.V. of about 4and 50% by weight coconut oil to give a good margarine oil. Thiscorandomized margarine can be modified by the addition of any soft oilor mixtures thereof.

While it is not desired to limit the operation of the present inventionto any particular theory, it is theorized that the presence of the longchain fatty acids containing 20 to 22 carbon atoms provides thestiffening power which improves the heat stability of the margarine. Thepresence of the short chain fatty acids containing 6 to 14 carbon atomson the same triglyceride molecule as the long chain fatty acids reducesthe melting point of the triglyceride but still allows retention of thestiffening properties of the triglyceride at room temperature, thusproviding an improved eating quality-heat stability balance.

The following examples are given to illustrate the present invention.

The margarines in the examples below were prepared by mixing themargarine oil with milk powder, salt and emulsifier in the followingmanner:

Eighty pounds of the margar'me oil being tested was melted and heated toF. in a hot water jacketed pilot plant mix tank. 1.65 pounds ofcommercial milk powder and 2 pounds of salt were mixed (slurried) in 15pounds of water. An emulsion was prepared from the margarine oil andfrom the milk slurry with an addition of 0.05 lb.

monoglycerides prepared from partially hydrogenated soybean oil.

The margarine emulsion was chilled through a conventional Votator A unitassembly and a B unit. Votators (chillers) are well-known in the art,but a description of such apparatus may be found at pages 921-924 of A.E. Bailey, Industrial Oil and Fat Products, 2nd Ed., IntersciencePublishers Inc, New York City, NY. (1951).

The extruded product was packed at approximately 40 F. and tempered asusual for 48 hours at 50 F.

Example 1 Forty parts of refined and bleached coconut oil were mixedwith sixty parts of refined and bleached palm oil and the mixturecorandomized.

A second blend was prepared which consisted of fifty parts refined andbleached coconut oil mixed with fifty parts refined and bleached highlyhydrogenated rapeseed oil having an I.V. of about 4 and corandomized.

The corandomization was carried out under the following conditions: Theoil mixtures were heated to 340 F. under a vacuum of about mm. mercuryand held under these conditions until dry. Catalyst was then added: thisconsisted of 0.22% glycerine plus 0.7% NaOH as 49% solution in water;but other catalysts such as sodium methylate may be used. The reactionwas carried out by maintaining the mixture at 340360 F. under about 10mm. mercury vacuum until corandomization was complete, as indicated bysamples taken and tested for SCI. Two successive samples showing closelyagreeing SCI values indicated completeness. After reacting as above, themixture was cooled to 140 F. Throughout the entire heating, reacting,and cooling periods the mixture was agitated mechanically and a streamof nitrogen was passed through it. After cooling, the mixture waswater-washed in an agitated kettle with about 4% of water, settled,decanted and then filtered.

The two blends were then mixed together with soybean oil which had beenhydrogenated to an I.V. of about 95 in the proportions shown below,deodorized at 200 C. and a margarine prepared as described above. Themargarines were tested by standard uniform testing procedures.Spreadability at 50 F. and eating quality were judged by a panel ofexperts and graded on a scale of 1 to 10, 1 being poor and 10 beingexcellent. Slump tests were also graded by a panel of experts on thesame grading scale against standard photographs. Oil off figures werequantitatively determined by measuring the oil lost by a margarinesample after 48 hours at 85 F. The reported figures are the calculatedpercentages of lost oil.

In Example 1, above, the proportion of short chain fatty acids havingfrom 6 to 14 carbon atoms derived from a corandomized blend of coconutoil and palm oil garine oil while the proportion of long chain fattyacids having from 20 to 22 carbon atoms derived from the rapeseed oilwas 1.8% by weight of the margarine oil. The ratio of short chain fattyacids (abbreviated SCFA) to long chain fatty acids (abbreviated LCFA) is15.6: 1.

These results indicate that the margarine prepared from a corandomizedblend of coconut oil and palm oil without the corandomized coconut oiland rapeseed oil additive gave a margarine which had a very goodspreadability, poor oil-off and a very low grade in the slump test. Onthe other hand, when the additive of the present invention was added tothe margarine oil and a margarine formed therefrom, there was no adverseeffect on the excellent spreadability, a significant improvement on theslump, and a dramatic improvement in the oil-off quality.

Examples 2 and 3 Control Example2 Example3 Coconut/palm corandomizedblend, percent:

Coconut Palm Coconut/palm/rapeseed co randomized blend, percent:

Coconut ooooum OQWO Rapeseed Soybean oil, percent The margarines weretested in the standard manner as described in Example 1 and the resultswere as follows:

Control Example2 Example? Spreadability Oil-ofi 85 F./48 hours, percentSlump Eating Quality (50 F.) SCI F.):

In Example 2, the proportion of SCFA derived from the 42.5% by weightcoconut oil is 34.2% by weight While the proportion of LCFA derived fromthe 5% by weight rapeseed oil is 1.8% by weight giving a ratio of SCFAto LCFA of 19:1. In Example 3, the proportion of SCFA derived from the36.0% by weight coconut oil is 29% by weight while the proportion ofLCFA derived from the 8.7% weight rapeseed oil is 3.1% by weight givinga ratio of SCFA to LCFA of 9.4:1. There are no significant quantities oflong chain or short chain fatty acids in palm oil or soybean oil;therefore, the ratio of SCFA to LCFA is calculated by taking the shortchain and long chain fatty acids in the coconut oil and rapeseed oil.

These results also show, as in Example 1, that the addition of theadditive of the present invention to a margarine oil gives a margarinein which there is no significant detrimental effect on the excellentspreadability, a significant improvement in the slump over a testmargarine oil, and a dramatic improvement in the oil-01f qualities.

Example 4 For the control product refined and bleached soybean oil washardened to an I.V. of about 81. Ninety parts of this were blended with10 parts of refined and bleached palm oil.

Control Example 4 Soybean oil (LV. 81), percent 90 O Soybean oil (LV;107), percent 65 Palm'oil, percent 10 0 corandomized blend percent:

Palm kernel oil 0 30. 8 Rapeseed oil. 0 4.2

The margarines were tested as described in Example 1 above, and theresults are given below:

Control Example 4 Spreadability (50 F.) 7. 0 7.5 Oil-ofi 85 F./48 hours,percent 4.2 1.0 Slump 5. 5 8.0 Eating Quality (50 F.) 7.3 7. 8 SCI (80F.):

At 50 F, 30. 4 28. 4

At 70 F- 16.2 17. 7

At 80 F 11. 3 1 1. 3

At 92 F 2. 7 3.2

In Example 4, the proportion of SCFA derived from the 303% by weightpalm kernel oil is 23.6% by weight while the proportion of LCFA derivedfrom the 4.2% by weight rapeseed oil is 1.4% by weight giving a ratio ofSCFA to LCFA of 1711.

These data also show the unusual elfect on the oil-ofi of the additiveof the present invention and illustrates that the eating quality may beimproved without sacrificing the other beneficial qualities of themargarine.

What is claimed is:

1. A margarine oil adapted to be manufactured into a margarine of goodspreadability, oil-off, slump and eating qualities comprising at leastabout 5% by weight of corandomized triglycerides containing saturatedshort chain fatty acids having from 6 to 14 carbon atoms and saturatedlong chain fatty acids having from 20 to 22 carbon atoms, the amount ofthe saturated long-chain fatty acids being bout 0.3% to about 5.0% byweight of the margarine oil, the ratio of the saturated short chainfatty acids in the margarine oil to the saturated long chain fatty acidsin the margarine oil being from :1 to 1:1.

2. The margarine oil of claim 1 wherein the balance of the portion ofsaid margarine oil which is not corandomized triglycerides is an oilselected from the group consisting of soybean oil, cottonseed oil, cornoil, sunflower seed oil, safilower seed oil, peanut oil, lard andmixtures thereof.

3. The margarine oil of claim 1 wherein the saturated long chain fattyacids are selected from the group consisting of rapeseed oil, mustardseed oil, Wallflower seed oil, nasturtium seed oil, marine oils andmixtures thereof, said oils being hydrogenated to an iodine value ofless than 30.

4. The margarine oil of claim 1 wherein the short chain fatty acids areselected from the group consisting of palm kernel oil, coconut oil, andmixtures thereof.

5. A margarine oil adapted to be manufactured into a margarine of goodspreadability, oil-0E, slump and eating qualities comprising at leastabout 5% by weight of corandomized triglycerides containing saturatedshort chain fatty acids having from 6 to 14 carbon atoms, said shortchain fatty acids being selected from the group consisting of palmkernel oil, coconut oil, and mixtures thereof, and saturated long chainfatty acids having from 20 to 22 carbon atoms, said saturated long chainfatty acids being hydrogenated to an iodine value of less than 10 andselected from the group consisting of rapeseed oil, mustard seed oil,Wallflower seed oil, nasturtium seed oil, marine oils, and mixturesthereof, the amount of the saturated long chain fatty acids being about1.0% to about 4.0% by weight of the margarine oil, the ratio of thesaturated short chain fatty acids in the margarine oil to the saturatedlong chain fatty acids in the margarine oil being 40:1 to 2:1.

References Cited UNITED STATES PATENTS 3,298,837 1/1967 Seiden 99-118 A.LOUIS MONACELL, Primary Examiner.

M. W. GREENSTEIN, Assistant Examiner.

1. A MARGARINE OIL ADAPTED TO BE MANUFACTURED INTO A MARGARINE OF GOODSPREADABILITY, OIL-OFF, SLUMP AND EATING QUALITIES COMPRISING AT LEASTABOUT 5% BY WEIGHT OF CORANDOMIZED TRIGLYCERIDES CONTAINING SATURATEDSHORT CHAIN FATTY ACIDS HAVING FROM 6 TO 14 CARBON ATOMS AND SATURATEDLONG CHAIN FATTY ACIDS HAVIN G FROM 20 TO 22 CARBON ATOMS, THE AMOUNT OFTHE SATURATED LONG-CHAIN FATTY ACIDS BEING BOUT 0.3% TO ABOUT 5.0% BYWEIGHT OF THE MARGARINE OIL, THE RATIO OF THE SATURATED SHORT CHAINFATTY ACIDS IN THE MARGARINE OIL TO THE SATURATED LONG CHAIN FATTY ACIDSIN THE MARGARINE OIL BEING FROM 100:1 TO 1:1.